Cellulose organic ester composition containing a butyl-p-toluene sulphonamide



Patented Oct. 11, 1938 tion agents, so that the resulting product will UNITED STATES-I f j jam.

PATENT OFFICE VCIELLULOSE ORGANIC ESTER'COMPOSITION CONTAINING A BUT PHONAMIDE YL-P-TOLUENE SUL- Henry B. Smith, Rochester, N. Y., assignor, by

memo assignments, to,

pany. J ersey City, N. J

c Jersey Eastman Kodak Coma corporation of New Nobrawing. ApplicationMay '31, .1934, I

Serial No.

. 14 Claims. (01. ree -my This invention .relates to compositionsofmatter in which an-organicesterotcellulose, such, for instance, as cellulose acetate, is combined or mixed with other substances, such as a'compatible plasticizer, with or without a common solvent for both, and with or without other useful addior film of desired thinness which are substantially waterproof, are unaffected by ordinary "photo.- graphic fluids and possess the ,desired properties of a 'support for. sensitive photographic coatings. Another object of my invention isto producecom positions which will not injure, or be injured by, the substances or surfaces with which they are associated during manufacture.v Other objects will become apparent to those skilled in the art to which this invention pertains.

"Whilefcellulose acetateohasbeenknownfor decades, it has also been known'thatto utilize it in j the various plastic arts it is .necessaryto mix therewith various pla'sticizing or conditioning agents. Certain of these and other additionj agents are also-added for the'purpose of reducing the infiammability of the product. Plastic 'in-' ducing agents, such as thehigher alcohols and their esters, are sometimes also added. Similarly, addition compounds of various kinds have been employed to increase flexibility, transparency, toughness and other properties'which will enhance the value of the resulting product. :Addiition products for the same or similar purposes" are also "added tolcellulose acetate to'prepareit for use-in the other plastic arts, such as in the manu facture of lacquers, varnishes, artificial silk filaments and the like. .While the plasticizers or other addition agents heretofore discovered have had their utility in the art, the increasing'use to which cellulose acetate has been put and the in-' creasing number of desirable properties required of cellulose acetate for most purposes have'made the di cov y r new nd. ec nom p s e ze e importance to the art. Tins has been a problem of some difflculty, since many of the nitrocellulose solvents are not;solvents for cellulose acetate, and many substances which act as plasticizers'for nitrocellulose. aresno't sufliciently compatible with cellulose acetate to be used asplasticizers in cellulose acetate compositions.

One of the'tplasticizers which has been used with cellulose. acetate is ethyl p-toluene sulphonamide. While it givesgood initial flexibility to cellulose acetate, films, films containing this plasticizer. do not maintain their flexibility over long periods of time, and hence are ,notentirely satisfactory, Iv have discovered, however, that, two

.related compounds, namely, n-butyl p-toluene fsul'ph'onamide'and :li-n-butyl p-toluene sulphon- I amide, have greatly superior properties as plasticizers for cellulose, acetate and other" cellulose .organic esters. They confer on cellulose acetate films, for example, initlal flexibilities comparable with-those conferred by ethyl p-toluene sulphonamide, but whereas cellulose acetate films plasticized with 20% of ethyl p-toluene sulphonamide became brittle withini30 days when keptat' 65 C films plasticized withonly 10% of di-n-butyl p-toluenesulphonamide or with from 10% to 50% (partsby weight based on the cellulose acetate) 01 n-butyl p-toluene sulphonamide maintained 'flexibilityior 198 days at 65 C.at least a 650% increase in flexible life of the film-thus indicating that they will withstand ordinary usage satisfactorily for many years.

n-butyl p-toluene sulphonamide has the structuralformula 1 and is ja new compound Itmay be prepared as follows: 219 g. (3 g.-mols) of n-butyl amine is placed in, a 3-liter flask together with one liter of water,:onelig. o1 benzene, andi600 g. (6 g.-'mols) o1=14o% sodium hydroxide solution. 571.5 g. (3 g.- molsYof'p-toluene sulphone chloride is added very slowly,-with constantstirring. Two or three or otheraddition agents a matter of considerable hours after the completion of the reaction, the

mixture is carefuIly-acidifled with glacial acetic.

acid: The -benzene1layer, which contains the product, is separated and vacuum distilled. The irflctlon boiling at 233-234 C. at 20 mm. pressure is collected, poured into 250 g. of ligroin, and cooled in an ice-salt bath. n-butyl p-toluene sulphonamide is obtained as white crystals, which are filtered off on a Buchner funnel. The compound melts at 41-42.5 C., and is very soluble in methanol and in 20% sodium hydroxide solution, but insoluble in ligroin.

Di-n-butyl p-toluene sulphonamide has the structural formula 1 o I omOg-mmnna and is a new compound. It may be prepared as follows: 285 g. (2 g.-mo1s) of: din-butyl'amine is placed in a 3-liter flask with one liter of water, one kg. of benzene, and 200 g; (2 g.-mols) of sodium hydroxide. To this mixture, 381 g. -(2g.- mols) of p-toluene sulphone chloride is added slowly, with constant stirring; over a period of" from two to three hours. When the reaction is complete, the water layer is madeslightlyi acid to litmus paper with glacial acetic acid, and sep-' arated from the benzene layer, which contains the product. The benzene is distilled off, and the fi-mbut -ioiuenc. am e, i distilled under re uc d e su Itxbbi a 2331- 34? at .20 mm re ure-'5 It sjv rrs ub e, in H r carbon tetrachloride, chloroform,- and methanol. j In order that those skilled in this art may better understand my invention, l would state, by way of illustration, thatfor thc manufacture of photographic film base or ,other'sheets,;my new compositions of matter may becompounded as follows; 100 parts; of acetone soluble cellulose acetate. i...e. cellulose. acetatecontainingfrom 36% 42% acetyl radical, .approximatfil is dissolved with stirring atfatmospheric temperature in 300 to 590 parts, preIerabIyAOQparts, by weightyof acetone; sTo this solution may be contributes ta the fini'shedp'roduct. The amount .fq r e i m il r s c? b n r sed 99 decreased, dependin upon whether itis desired to have a more or less freely flowingcompo'sithin, respectively. Comp o sitions of matter so prepared may be deposited'uponanysuitable filni io'rming surface to form films or sheets; in a manner'well kngwntdthos'e skilledin-the art. Films so produced have permanently brilliant transparency, and are tough as well as flexible.

Other similar solvents (instead of acetone) which are compatible with the cellulose acetate and my new plasticizers may also occur'to those skilled in this art, such, for instance, as ethlyle'ne chloride-alcohol mixturesf In like manner these plasticizers may be compounded with other single organic esters of" cellulose, ,such as cellulose ,propionate, butyrate and the like, or with mixed organic esters, such as cellulose acetoes'tearate,

cellulose .aceto-propionate or .cellulose acetomi a s b so v tflwhiieh. W ll dissolve botli the cellulosede'rivative and, the plasticizer being employed. a

I Inasmuch as my above de'scribed"compositions of matter are useful'in the production of'films and sheets, it will be'apparent that mynew plasticizers may also be employe'd'with advantage in the other branches of the plastic art. It may be desired to employ compositions 'of different viscosity or evaporation characteristics, but this is a mere matter of changing the solvent proportion or adding evaporation retardents or other high or medium-boiling constituents, as has been well known in the art for more than a decade.

My novel plasticizers may be employed with advantage in connection with a number of the known lacquer and varnish formulae with which they may be found to be compatible. In such cases the plasticizer is usually first put into solution with the cellulose derivative solution,

1 and if non-solvents are added for the purpose of cheapening the composition, they are added only to such an extent as will not precipitate the derivative from solution. Other uses within the scope of my invention will also suggest them- "selves' to those,{skil1ed in the art and are to be included within the scope of the appended claims.

What i clairn' as my invention and desire to be secured by Letters Patent of the United States 1s: Ty

1. is composition of matter comprising a. cellulose organic acid ester and as a plasticizer therefore. butyl p'-toluene sulphonamide.

2. A composition of matter comp-rising cellulose acetate and asa plasticizer therefor a butyl p-toluen'e' sulphonamide.

3.*A composition of matter comprising" cellulose acetate and as a plasticizer therefor n-butyl "pf-'toiuene' suiphonamide. f

J41 A'composition of 'matter comprising cellulose acetate and as a plasticizer therefor di nbutyl p-toluene sulphonamide.

5. A composition of matter comprising 100 parts of cellulose acetate. and as a plasticizer thereror about "10 to parts, by weig'ht, of

n b'utyl p-tolue'ne sulpho'namide.

6. 'A composition of matter comprising 100 parts of cellulose acetate and as a plasticizer thereforabout 1 0 "parts, by weight, of di-ri butyl p-toluene s'ulpl'ionamide. t V

4 7. A" transparent, flexible sheet comprising a cellulose organic acidesteran'd, as a plasticizer therefor, a butyl pf-toluen' r I sulphonamide, *3. 'A' transparent, flexible sheet comprising 'celii-butyl p-toluen'e sulphonamide.

10; 'A transparent; flexible sheet comprising 100 parts 1 of cellulose, acetate and, as a' plasticizer therefor,'about 10 parts, by'weight, of di-n-butyl p-toluene'sulphonamide; l1; Anew composition of matter comprising a cellulose derivative base and a butyl p-toluene sulphonainide;

12.'A composition of matter "comprising cellulose acetate and-a monobutyl p-toluene suiphon amide. 13. A composition of matter comprising 100 parts ;of cellulose acetate and about 10 to 50 parts, by weight, of a"monobut'yl p toluene sulphonar'nide; I

14. A transparent, flexible sheet comprising 100 parts" of cellulose acetate and, as a plasticizer thereforf'about 10 t 50 parts, b y'weight, of a monobutyl p-toluene sulphon'amide.

HENRY B. SMITH.

'lul'oseacetate andQ'as a plasticizer therefor, a

CERTfFiCATE OF CORRECTION.

' Patent No. 2,1 2, 8L October-ll 19 HENRY BQSMITH. 'It is hereby certifid-that errdr appearg in the printed. s pecific ation of the apove numberedjpatent requiring cpzgrctioh as fdllowg: Page 2, .firt

column line 11 ifor the ninneral 285" read 258} that @311 SE16: Letters form to the record of the case in -th e Patent office Signedand sealed this 6m day of December, A. D. 1958-.

(Seal) ActiLng' (lnnnisioher oif' Patents. 

